Insecticidal compositions and methods of combatting insects using cyclopropane carboxylate insecticides with a synergistic compound of mono (alkyl and alkenyl) mono omega-alkynyl arylphosphonates

ABSTRACT

Synergistic insecticidal combinations of esters of certain cyclopropanecarboxylic acids, e.g. pyrethrins, allethrin, and related compounds, with mono(alkyl and alkenyl) mono- omega alkynyl aryl- and aralkylphosphonates are described. The preparation and properties of representative members of this new class of synergistic phosphonates are described, and test results of their synergistic combinations with representative cyclopropanecarboxylates are reported.

United States Patent Montgomery et al.

[ 51 May 20, 1975 INSECTICIDAL COMPOSITIONS AND METHODS OF COMBATTINGINSECTS USING CYCLOPROPANE CARBOXYLATE INSECTICIDES WITH A SYNERGISTICCOMPOUND OF MONO (ALKYL AND ALKENYL) MONO OMEGA-ALKYNYL ARYLPHOSPHONATESlnventors: Ronald Eugene Montgomery,

Middleport; Harry Hobart Incho, Medina, both of NY.

Assignee: FMC Corporation, New York, NY.

Filed: Oct. 2, 1972 Appl. No.: 294,238

Related US. Application Data Division of Ser. No. 122,168, March 8,1971, Pat. No. 3,709,988, which is a division of Ser. No. 800,264, Feb.18, 1969, Pat. No. 3,652,741, which is a continuation-in-part of Ser.No. 630,204, April 12, 1967, abandoned, which is a continuation-in-partof Ser. No. 559,422, June 22, 1966, abandoned, and Ser. No. 624,689,March 21, 1967, abandoned.

US. Cl. 424/192; 424/219; 424/274; 424/285; 424/306 [51] Int. Cl. A0ln9/08; AOln 4/36 I [58] Field of Search 424/186, 219, 187, 192

[56] References Cited UNITED STATES PATENTS 3,065,125 11/1962 Newallis424/219 3,212,964 10/1965 Sehring et a] 424/186 3,485,916 12/1969Neumeyer et al. 424/186 Primary Examiner-V. D. Turner AssistantExaminerA1len J. Robinson [5 7 ABSTRACT 11 Claims, No Drawings 1INSECTICIDAI. COMPOSITIONS AND METHODS OF COMBATTING INSECTS USINGCYCLOPROPANE CARBOXYLATE INSECTICIDES WITH A SYNERGISTIC COMPOUND OFMONO (ALKYL AND ALKENYL) MONO OMEGA-ALKYNYL ARYLIHOSPI'IONATES CROSSREFERENCE TO RELATED APPLICATIONS This application is a division of Ser.No. 122,168, filed Mar. 8, 1971, now U.S. Pat. No. 3,709,988, which is adiv. of Ser. No. 800,264 filed Feb. 18, 1969, now U.S. Pat. No.3,652,741, which is a continuation-inpart of Ser. No. 630,204 filed Apr.12, 1967, now abandoned, which is a continuation-in-part of Ser. No.559,422 filed June 22, 1966 and Ser. No. 624,689 filed Mar. 21, 1967,both now abandoned; and is related to copending applications Ser. No.559,745 filed June 23, 1966, Now U.S. Pat. No. 3,555,123, and Ser. No.634,121 filed Apr. 27, 1967, now U.S. Pat. No. 3,557,259, which arecontinuations-in-part of Ser. No. 540,175 filed Apr. 5, 1966 and Ser.No. 559,412 filed June 22, 1966, respectively, both now abandoned.

BACKGROUND OF THE INVENTION Among the most widely used insecticidestoday are the pyrethrins, the active principle of pyrethrum flowers(Chrysanthemum cinerariaefolium), which have a high order ofinsecticidal activity and a low mammalian toxicity. The relatively highcost and the uncertain supply of pyrethrins have encouraged attempts toprepare synthetic insecticides which retain the desirable properties ofpyrethrins. It has long been known that synthetic products having abasic structural similarity to pyrethrins in that they are esters ofcertain substituted cyclopropanecarboxylic acids, in particular 2,2-dimethyl-3-( 2-methylpropenyl)cyclopropanecarboxylic acid (which is alsoknown as chrysanthemumic acid and will be so referred to herein),exhibit insecticidal activity of a significant order.

The wide market which pyrethrins and related synthetic insecticidesenjoy today is due primarily to the discovery of certain additives whichenhance the activity of these insecticides These additives, commonlycalled synergists, are agents which may or may not themselves exhibitinsecticidal activity, but which when combined with pyrethrins orrelated compounds produce new insecticides, having an effectivenesssignificantly greater than the sum of theeffe ctiveness of thecomponents when used separately. A great deal of time and effort hasbeen devoted to the search for effective synergists. One of the mosteffective and most widely used of the pyrethrins synergists is thecompound piperonyl butoxide, which is described in synergisticcombination with pyrethrins in Wachs U.S. Pat. No. 2,550,737.Unfortunately, it has been found that many compounds which are excellentsynergists for pyrethrins are not nearly as effective when used withallethrin or other synthetic cyclopropanecarboxylic acid esters.

SUMMARY OF THE INVENTION This invention relates to novel compositionsfor the control of insects and acarids and in particular to suchpesticidal compositions containing pyrethrins, allethrin, or relatedinsecticidal cyclopropanecarboxylic acid esters, in combination withcertain mono( alkyl or alkenyl) mono-m-alkynyl arylandaralkylphosphonates as synergists for insecticidal activity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The synergistic phosphonates ofthis class have the structural formula:

wherein R is an alkyl, alkenyl, or alkoxyalkyl group of from one toabout twenty carbon atoms, straight or branched chain; R is an alkylenegroup of one to six carbon atoms, straight or branched chain; R ishydrogen or methyl; n is an integer from 0 to 3 inclusive; Ar is anaromatic radical such as phenyl, pyridyl, thienyl, pyrryl, furanyl,isothiazyl, and the corresponding benzoderivatives; Y is halogen; -m isan integer from 0 to 2 inclusive; and X is oxygen or sulfur. When n is 2or 3, the R groups may be the same or different. Similarly, when m is 2,the Y groups may be the same or different.

Particularly preferred are those compounds represented by the followingformulae:

/OR1 P DRnCE-CH 0am wherein R is an alkyl or alkenyl group of from oneto about six carbon atoms; R is an alkylene group of from one to fourcarbon atoms; Y is chlorine or fluorine; and m is an integer from 0 to2inclusive.

Of the natural and synthetic esters of cyclopropanecarboxylic acids thebest known members, preferred for use herein because of their generalinsecticidal activity and availability, are the esters ofchrysanthemumic acid, which have the general structure:

and

on, R10!!! cu=c (cm):

and wherein the radical R, can be any of the very large number ofradicals which have found to form insecticidal chrysanthemumates. Forexample, this class of esters includes the pyrethrins, allethrin(3-allyl-2-methyl- 4-oxo-2-cyclopentenyl chrysanthemumate) and relatedinsecticides as described by Shechter and La Forge in U.S. Pat. No.2,661,374; cyclethrin (3-(2-cyclopentenyl)-2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate) asdescribed by Guest and Stansbury in U.S. Pat. No. 2,891,888; furethrin(3-furfuryl-2- methyl-4-oxo-2-cyc1opentenyl chrysanthemumate) asdescribed in National Distillers Products British Pat. Specification No.678,230; barthrin (6-chloropiperonyl chrysanthemumate) and its bromoanalog, as described by Barthel et al in U.S. Pat. No. 2,886,485;dimethrin (2,4-dimethylbenzyl chrysanthemumate) and the 3,4- dimethylisomer, as described by Barthel in U.S. Pat. No. 2,857,309; compounds ofthe class of (cyclohexene-l ,2-dicarboximido)methyl chrysanthemumates asdescribed in Belgian Pat. No. 646,399 and(cyclohexadiene-l,2-dicarboximido)methyl chrysanthemumates as describedin Belgian Pat. No. 651,737. both to the Sumitomo Chemical Company, Ltd;and related compounds such as phthalrnidoalkyl and substitutedphthalimidoalkyl chrysanthemumates as described in Sumitomo Belgian Pat.No. 635,902. Other insecticidal esters of ,chrysanthemumic acid alsoform synergistic combinations with the phosphonates of this invention.

Synthetic esters of other cycloprop'anecarboxylic acids, closely relatedto chrysanthemumic acid, but having some variation in the substituentson the cyclopropane ring, have also been found to have insecticidalactivity. Esters of this class are described in Netherlands ApplicationNo. 67,11587 to Sumitomo Chemical Company, Ltd. and in Belgian Pat. No.690,984 to National Research Development Corporation. The usefulinsecticides of this class, which form synergistic combinations with thephosphonates of this invention, include esters of2,2,3,3-tetramethylcyclopropanecarboxylic acid, particularly(-benzyl-3-furyl)methyl 2,2- ,3,3-tetramethylcyclopropanecarboxylate.

The preparation of the phosphonates of this invention and theirsynergistic insecticidal properties are illustrated in the followingexamples, which are not intended to be limitative of the variety ofprocedures which are applicable to the synthesis of mono(alkyl oralkenyl) mono-w-alkynyl phosphonates, or of the many insecticidalcombinations in which they are effective. In these examples, alltemperatures are in degrees centigrade.

EXAMPLE 1 Preparation of Butyl 3-Butynyl Phenylphosphonate The startingmaterial, butyl phenylphosphonochloridate, was prepared fromdichlorophenylphosphine as follows: To a cold, stirred solution of 30.0g of butanol and 41.4 g of triethylamine in about 300 ml of ethyl etherwas added dropwise a solution of 34.6 g of dichlorophenylphosphine inabout 200 ml of ethyl ether while the temperature was maintained below0. When addition was completed, the mixture was allowed to warm to roomtemperature. Stirring was continued overnight. The mixture was filtered,and the filtrate was concentrated under reduced pressure. The residualoil was distilled under reduced pressure to give 39.5 g of dibutylphenylphosphonite, b.p. '120131/ca 1.0 mm.

. Chlorine gas was bubbled into 38.5 g of dibutyl phenylphosphonite forabout 3 hours. The mixture was warmed to 50 under aspirator vacuum toremove butyl chloride. The residual colorless oil was dissolved in 100ml of benzene, washed with 1% sodium hydroxide and with water, driedover magnesium sulfate, and the dried solution concentrated underreduced pressure to give 30.6 g of pale yellow butylphenylphosphonochloridate. 1

A solution of 15.6 g of butyl phenylphosphonochloridate in ml of benzenewas added dropwise with stirring to a cold solution of 5.2 g of3-butyn-1-ol and 7.5 g of triethylamine in 45 ml of benzene while thetemperature of the mixture was kept below 10. When addition wascomplete, the mixture was slowly warmed to approximately 50 at whichtemperature it was stirred for one hour, then allowed to stand overnightat room temperature. The mixture was filtered, and the filtrate waswashed with dilute hydrochloric acid, dilute so- Analysis: Calcd forC,.,H, O;,P: C, 61.41; H, 7.53: Found: C, 6l.6l; H, 7.55.

EXAMPLE 2 The Synergistic Activity of Butyl 3-.Butynyl PhenylphosphonateThe synergistic insecticidal activity of butyl 3-butynylphenylphosphonate in combination with representative insecticidalcyclopropanecarboxylates, e.g. chrysanthemumates, was determined by thefollowing procedure: The test compound and the cyclopropanecarboxylatewere dissolved in parts by volume of acetone, which was then made up toparts by volume by addition of water. A group of 30 to 40 houseflies(Musca domestica L.), immobilized under carbon dioxide, was placed on amoist filter paper on a Buchner funnel attached to a vacuum source.Twenty-five ml of test solution was poured over the immobilized flies,this being sufficient volume that all flies were completely immersed.Vacuum was then applied to remove the test solution, and the flies weretransferred to holding cages lined with absorbent paper. Mortalitycounts were made after 24 hours. Results are shown in Table 1. In thisand subsequent tables, the amounts of the test ingredients are stated inconcentration terms of mg per 100 ml of test solution.

Table 1 Synergistic Compositions of Butyl 3-Butynyl PhenylphosphonateMortality of Cyclopropanecarboxylate mg Synergist mg HousefliesAllethrin 10 50 100% none 50 38% 10 none 34% l-Cyclohexene-1,2 10 50 I100% dicarboximido)methyl none 1 50. 38% chrysanthemumate 1 none 28% Theresults in Table 1 illustrate the synergistic interaction of aphosphonate of this invention with two different syntheticchrysanthemumates.

EXAMPLE 3 Table 2 EXAMPLE 5 The Synergistic Activity of Propyl2-Propynyl Phenylphosphonate The synergistic insecticidal activity ofpropyl 2- Chrysanthemumate mg Synergist mg iii'isliiei propynylphenylphosphonate in combination with allethrin, pyrethrins, and(l-cyclohexene-l,2-dicarbox- 72 98% imido)methyl chrysanthemumate wasdetermined by none 72 2% the test procedure of Example 2. Results areshown in 14.4' none 10 Table 3 v I Pyrethnns 14.4 72 82% i??? "lie 52Table 3 (1-Cyclohexene-l.2 14.4 72 100% I gmirslgggrgdslzrgtecthy nzn leCompositions 02:30 kyll yglgrtg gylnyrlnlzlieesnylphosphonate Mortalityof The results shown in Table 2 are illustrative of the gen-Chrysanthemum "j synerg'st mg eral synergistic interaction between analkyl w-alknyl Allethrin 10 50 100% phenylphosphonate of this inventionand chrysan- 2 themumates. Even at dosages of 72 mg this phospho-Pyrethrins 1o 20 100 0 nate itself was essentially inactive, yet aconsistent and 50 substantial synergistic effect was observed incombina- (bcyclohexengm 10 1 tions with chrysanthemumates whichthemselves prodicarboximidmmethyl 50 0 chrysanthemumate 10 none 12%duced negligible kill of houseflies under these test conditions.

EXAMPLE 4 Preparation of Propyl 2-Propynyl Phenylphosphonate Propylphenylphosphinate used in the preparation of this synergist was preparedby the method of Kosolapoff, J.A.C.S.72, 4292 (1950). Phenylphosphonousdichloride, 126.1 g, was added dropwise with stirring and coolingto 127g propyl alcohol over' a period of minute s". The reaction mixture wasallowed towarm to room temperature. After stirring at room temperaturefor 2 hours, the reaction mixture was warmed to ,'40-50 and stirred for1 hour. Excess propyl alcohol During this addition the temperature waskept below When addition was complete, the reaction mixture was warmedto room temperature, and stirring was continued for 15 hours.Precipitated triethylammonium bromide was removed by filtration and thefiltrate washed successively with dilute hydrochloric acid, dilutesodium hydroxide, and water. The washed organic layer was dried overmagnesium sulfate, and after removal of the drying agent, stripped ofsolvent under reduced pressure, leaving 13.1 g of light yellow oil. Theproduct was distilled (diffusion) with a bath temperature of l09-l 18 atOlly. Hg. giving 10.4 g-of propyl 2-propynyl phenylphosphonate as aclear, colorless oil.

Table 3 shows that propyl 2-propynyl phenylphosphonate, itself inactiveat the dosage used, is an effective synergist for a variety ofchrysanthemumates.

EXAMPLE 6 The synergistic activity of propyl 2 -propynylphenylphosphonate with a variety of chrysanthemumate esters againsthouseflies was further demonstrated using the test procedure of Example3. Results are shows in Table 4.

Table 4 Compositions of Prcpgl2-Propynyl Phenylphosphonate andrysanthemumates Mortality of Chrysanthemumate mg Synergist mg HousefliesAllethi'in 14.4 t 72 71% none 72 4% 14.4 none 10% Pyrethrins 14.4 72 84%none 72 4% 14.4 none 8% (l-Cyclohexene-l,2- I 14.4 72 100%.dicarboximido)methyl none 72 4% ,chrysanthemumate 14.4 none 7%,

EXAMPLE 7 Preparation of sec-Butyl 2-Propynyl Phenylphosphonate Theintennediate sec-butyl phenylphosphinate was prepared as follows: Undera nitrogen atmosphere 25.9 g-phenylphosphonous dichloride was addeddropwise with stirring to 32.2 g se'c-butyl alcohol. During the 20 of3.4 g 2-propyn-l-ol, 9.4 g carbon tetrachloride, and 6.2 g triethylaminein 100 ml benzene. During addition the reaction mixture was kept at1520, then allowed to warm to room temperature and stirred overnight.Precipitated triethylammonium chloride was removed by filtration and thefiltrate washed successively, twice with 1% hydrochloric acid, one with0.5% sodium hydroxide, and twice with water. The washed organic layer,dried over magnesium sulfate, was stripped of solvent under reducedpressure and then subjected to high vacuum with vigorous stirring atroom temperature for six hours. The resulting oil, 8.0 g, identified assec-butyl 2-propynyl phenylphosphonate by infrared spectroscopy, was 98%pure by vapor phase chromatography.

Analysis: Calc'd for C H O P: C, 61.89; Found C, 62.10;

EXAMPLE 8 Preparation of Isobutyl 2-Propynyl Phenylphosphonate Followingthe procedure described in Example 7,

' 25.9 g phenylphosphonous dichloride was reacted with Analysis: C H OP: C, 61.89, H, 6.79; P, 12.28; Found: C, 61.68; H, 6.71; P, 12.05.

EXAMPLE 9 Preparation of Ethyl 4-Pentynyl Phenylphosphonate Followingthe procedure described in Example 1, 5.85 g 4-pentyn-l-ol -was reactedwith 11.3 g ethyl phenylphosphonochloridate. The final product, ethyl4-pentynyl phenylphosphonate, distilled (diffusion system) at a bathtemperature of 120-130 at 0.01 mm. Hg.

Analysis: Calcd for CmHnOaPi C, 6

Found: C, 6

EXAMPLE 10 I Preparation of n-Butyl 3-Butynyl Z-ThienylphosphonateFollowing the procedure described in Example 4, 4.0 g of 3-butyn-1-olwas reacted with 10.3 g of n-butyl 2- thienylphosphinate. The product,n-butyl 3-butynyl 2- thienylphosphonate, was distilled in short pathdiffu 8 sion apparatus at 0.511 Hg. with a bath temperature of 128l40.r1 1.5069.

Analysis: Calcd for C H O PS: C, 3 l 1.4

52 P, 7; Found: C, 53 P, 8

EXAMPLE 1 1 Preparation of n-Octadecyl B-Butynyl Phenylphosphonate IAnalysis: Calcd for C H O P: Found:

EXAMPLE 12 Preparation of Propyl 2-Propynyl Benzylphosphonate Theintermediate 2-propynyl benzylphosphonochloridate was prepared through aseries of reactions starting with diethyl benzylphosphonate as set forthbelow.

In a flask equipped with heating mantle, stirrer, and reflux condenserwere combined 1,000 g diethyl benzylphosphonate and 3.8 liters of 12Nhydrochloric acid. After the stirred mixture was heated to 65, enoughdioxane (200210 ml) was added to give a clear solution. The solution wasstirred and refluxed for 64 hours. When the solution was cooled to 4550,a solid separated out. The filtered solidwas dried in a vacuum oven at-74 for 15 hours, giving a yield of 703 g. benzylphosphonic acid, m.p.l71173.

In a flask equipped with a stirrer, reflux condenser, drying tube, solidaddition funnel, and gas scrubber, a slurry of 111.5 g benzylphosphonicacid in 1 l hexane was stirred and warmed to 35-40. When the first 50 gportion of a total of 259 g PC1 was added to the mixture, reactionstarted immediately as evidenced by evolution of HCl. The reactionmixture was then cooled to room temperature, and the balance of the PCladded in 50 g portions over a period of about 2 hours, during which timethe temperature increased to 60. After the reaction mixture cooled toroom temperature, S0 was bubbled through the mixture for 15 minutes toremove HCl. After removal of solvent under reduced pressure, the productwas distilled in a short path still (pressure 0.01 mm., pot temperature-125) to give 123.7 g benzylphosphonic dichloride.

Dipropyl benzylphosphonate was prepared by dropwise addition of 62 gbenzylphosphonic dichloride in 200 ml benzene to a stirred solution of39.3 g n-propyl alcohol and 65.9 g triethylamine in 400 m1 benzene.After stirring overnight the reaction mixture was filtered to removetriethylammonium chloride. The filtered solid was washed with benzene,and the washings added to the filtrate. The clear benzene solution waswashed four times with ml portions of 1% hydrochloric acid, twice with100 ml portions of 1% sodium hydrozide, and finally with 100 ml water.The solution was then dried over magnesium sulfate. After removal ofsolvent under reduced pressure, the product was distilled in a shortpath still (pressure 0.06 mm., bath temperature 1 l5l28) to give a totalyield of 47 g dipropyl benzylphosphonate, n 1.4883, identified by infra-5 red spectral analysis.

Analysis: Calc'd for C H Q-P: C 60.93; Found: C 60.97;

Propyl benzylphosphonate was prepared from the intermediate dipropylester as follows: 45 g dipropyl benzylphosphonate 39 g sodium hydroxide,and 350 ml distilled water were stirred at reflux temperature for 20hours, during which period the cloudy reaction mixture became clear.When the pH was adjusted to 1 by dropwise addition of about 125 mlconcentrated hydrochloric acid, a solid precipitate formed. Since thesolid liquified during an attempt at filtration, the product was takeninto solution by three successive extractions of the reaction mixturewith 200 ml portions of chloroform. After the combined extracts weredried over magnesium sulfate, solvent was removed under reduced pressureto give a viscous, cloudy liquid. Further subjection to vacuum gave 37.5g of sticky, white solid, propyl benzylphosphonate, used in thefollowing synthesis step.

Propyl benzylphosphonochloridate was prepared as follows: Under anitrogen atmosphere, in a flask equipped with a stirrer, gas inlet tube,condenser, and gas scrubber, 37.5 g propyl benzylphosphonate and 94 gthionyl chloride were stirred at 4050 for 4 /2 hours. To aid in theremoval of any volatile by-products, two successive 100 ml portions ofbenzene were added to the reaction mixture at room temperature and thenremoved under reduced pressure. Further, subjection to vacuum gave 40.4g of amber colored liquid, identified by infrared spectroscopy as propylbenzylphosphonochloridate.

The synergist propyl 2-propynyl benzylphosphonate was prepared asfollows: In a flask equipped with a stirrer, a condenser fitted with adrying tube, and a dropping funnel, 20.5 g propylbenzylphosphonochloridate in 50 ml benzene was added dropwise, over aperiod of 30 minutes, to a stirred solution of 5.5 g 2-propyn-1-ol and9.8 g triethylamine in 100 ml benzene. After stirring at roomtemperature for about hours, the solution was filtered free oftriethylammonium chloride, and washed twice with 50 ml 1% sodiumhydroxide and once each with 50 ml 1% hydrochloric acid and 50 ml water.The solution was dried over magnesium sulfate and the solvent removedunder reduced pressure to give an amber colored oil. The crude productswas distilled in a molecular still (00001-000015 mm Hg, both temperature120C) to give 14.5 g propyl 2- propynyl benzylphosphonate, a lemoncolored oil, 11 1.5074.

Analysis: Calcd for C H O P: C 61.

Found: C 61.

EXAMPLE 13 Preparation of Propyl 3-Butynyl Benzylphosphonate Followingthe procedure of Example 12, 9.9 g propyl benzylphosphonochloridate wasreacted with 6.6 g of 3-butyn-l-ol and 9.5 g triethylamine to give 15.6g propyl 3-butynyl benzylphosphonate, identified by infrared spectralanalysis. r1 1.5052.

Analysis: Calc'd for c m o r; c

63.15; H 7.1 Found: C 63.04; H 7.4

Example 14 Preparation of Ethyl 2-Propynyl Benzylphosphonate Theprocedure of Example 12 was used to prepare ethyl 2-propynylbenzylphosphonate, identified by infrared spectral analysis n 1.5124.

Analysis: Calcd for C, H =,O P: C Found: C

EXAMPLE 15 Preparation of Ethyl 2-Propynyl 4-ChlorobenzylphosphonateAnalysis: Calcd for C H CIO P: C 52.86; H 5.18; P 11.36;

Found: C 53.14; H 5.36; P 11.15

EXAMPLE 16 Preparation of=Propy1 2-Propynyl 4-ChlorobenzylphosphonateFollowing the procedure of Example 15, 2propynyl4-chlorobenzylphosphonochloridate was reacted with give propyl2-propynyl identified by infrared n-propyl alcohol to4-chlorobenzylphosphonate, spectral analysis, n 1.5174.

Analysis: Calcd for C H ClQ-J: C 54.46; H .63;

5 10.80; Found:C 5.1; 4.

P Pl1.1

EXAMPLE 17 Preparation of Propyl 2-Propynyl3,4-Dichlorobenzylphosphonate The procedure of Example 12 was followedexcept that 3,4-dichlorobenzylphosphonic dichloride was pre- EXAMPLES 18TO 43 ag by lik gf la i g f P3 1 Following the general procedureexemplified above,

( h i a 662 st 3 f i 2: y a large number of compounds of this class arereadily g g g roguct g {2 er an 4 i 1 synthesized. The synergisticactivity of typical phos- Z l o hgnate g i a i phonates of thisinvention, in combination with typical 2' sispn 25 1 3 y n rare Spec raand useful insecticidal cyclopropanecarboxylates is fury D therillustrated in Table 5. These results were obtained following theprocedure described in Example 2.

EXAMPLE 44 Analysis; Calcd for C,,,H ,,Cl O P: C 48.62; H 4.71; P 9.64;The synergistic activity of the phosphonates of this Found: C 48.34; H450; P 9.54.

invention with chrysanthemumates over a wide range Table 5 Synergisticlnsecticidal Compositions Mortality Cyclopropanecarboxylate mgPhosphonate mg of Houseflies (1-Cyc1ohexene-1,2- 1O Methyl 2-propyny1 50100% dicarboximido)methy1 none phenylphosphonate 50 O chrysanthemumate10 none 1 1% Pyrethrins 10 Methyl 3-butyny1 50 100% nonephenylphosphonate 50 10 none 3% Allethrin 10 Ethyl 3-butynyl 100% nonephenylphosphonate 5O 36% 10 none 8% Allethrin 1O Ethyl 4-pentyny1 50 79%none phenylphosphonate 5O 0 10 none 8% Pyrethrins 1O Ethyl 3-butyny1 50100% none benzylphosphonate 50 7% 1 10 none 3% Pyrelhrins 1O Ethyl4-pentyny1 50 100% none benzylphosphonate 50 38% 10 none 3% Allethrin 10Ethyl 3-butyny1 50 100% none 4-fluorobenzyl- 5O 8% 10 phosphonate none8% (1-Cyc1ohexene-1,2- 10 n-Propyl 3-butyny1 50 100%dicarboximido)methy1 none phenylphosphonate 50 12% chrysanthemumate 10none 12% Pyrethrins 1O n-Propy14- 50 100% none pentynyl phenyl- 50 3% 10 phosphonate none 3% Allethrin 10 i-Propyl 2- 50 100% none propynylphenyl- 50 O 10 phosphonate none 33% (1-Cyc1ohexene-L2- 10 Z-Propenyl 2-50 100% dicarboximido)methyl none propn lphcnyl- 5O 3% chrysanthemumate1O phosp onate none 11% Pyrethnns 10 2-Propeny1 3- 50 none butynylphenyl- 50 O 10 phosphonate none 7% 1-Cyc1ohexene-l,2- 10 n-Butyl3-butynyl 50 dicarboximido)methyl none Z-thienylphosphon- 50 26%chrysanthemumate 10 ate none 24% (l-Cyclohegrene-LZ- l0 n-Pentyl 2- 50100% dicarboximldo)methyl none propynyl phenyl- 50 19% chrysanthcmumate10 phosphonate none 28% Allethnn 10 n-Pentyl 3-butyny1 50 100% nonephenylphosphonate 50 0 10 none 39% (l-Cyclohexene-LZ- 10 n-Pentyl 4- 50100% dicarboximido)methy1 none pentynyl phenyl- 50 O chrysanthemumate 1Ophosphonate none 28% Allethnn 10 n-Dodecyl 3- 5O 84% none butynylphenyl- 5O 3% 10 phosphonate none 33% Allethrin 10 n-Octadecy] 3- 50 93%none butynyl phenyl- 50 10% l0 phosphonate none 19% Pyrethnns 1Osec-Butyl 2- 50 100% none propynyl phenyl- 50 7% l0 phosphonate none 31% Pyrethrins 1O lsobutyl 2- S0 100% none propynyl phenyl- 50 0 10phosphonate none 31% Allethrin 1O n-Propyl 2- 50 100% none propynylbenzyl- 50 4% l0 phosphonate none 7% Pyrethrins 10 n-Propyl 3- 50 100%none butynyl benzyl- 5O 3% 10 phosphonate none 7 1% Table 5 ContinuedSynergistic lnsecticidal Compositions Mortality Cyclopropanecarboxylatemg Phosphonate mg of Houseflies l-Cyclohexene-LZ- 10 Ethyl 2- 50 100%dicarboximido)methyl none propynyl benzyl- 50 3% chrysanthcmumate lphosphonate none 35% Allethrin l0 Ethyl 2- 50 100% none propynyl 4 50 0l0 chlorobenzylnone 3% phosphonate' Pyrethrins l0 n-Propyl 2- 50 100%none propynyl 4- 50 3% l0 chlorobenzylnone l 1% phosphonate(l-Cyclohexene-l .2- 1O n-Propyl 2- 50 100% dicarboximido)methyl nonepropynyl 5O chrysanthemumate l0 3,4-dichloronone 35% benzylphosphonateof chrysanthemumate to Synergist ratios was demon- EXAMPLE 45 strated bya series of tests carried out by the method described in Example 2.Results for two different chrysanthemumate-synergist combinations areshown in Table 6.

Synergistic activity over a wide range of cyclopropanecarboxylate tosynergist ratios was further demonstrated by a series of tests ofrepresentative Table 6 Compositions With Different Chrysanthemumate ToSynergist Ratios mg. Chrysanatio Mortalit themumate( A) 7 mg. Synergist(B) A:B of Houseflies Compo- Composition 1 sition 11 5 none 9% 13% 5 101:2 83% 61% 5 1:5 100% 78% 5 50 1:10 100% 97% 5 100 1:20 100% 100% 5 2501:50 100% 100% none 100 8 23% none 250 3% 41% Composition 1:Chrysanthemumate l-cyclohexenel ,2-dicarboximido)methyl ch santhemumateSynergist propyl 2-propyny phenylphosphonate allethrin hutyl 3-butynylphenylphosphonate Composition 11: Chrysanthemumate- Synergist Table 7(5-Benzyl-3-furyl)methy1 2,2,3,3-Tetramethylcyclopropanecarboxylate inSynergistic Compositions Synergist 11: lsobutyl Z-propynylphenylphosphonate Synergist 111: Propyl S-butynyl benzylphosphonate Theresults in Table 6 illustrate the marked synergistic interaction foundover a wide range of ratios.

phosphonates of the invention with (5-benzyl-3- furyl)methyl2,2,3,3-tetramethylcyclopropanecarboxylate. The test method was asdescribed in Example 2, but with lower concentrations owing to the highlevel of activity of the cyclopropanecarboxylate. Results are shown inTable 7.

EXAMPLE 46 The effectiveness of synergistic compositions of thisinvention is strikingly shown in aerosol formulations, as illustrated inthe following examples: Aerosol formulations were prepared containing atypical insecticidal chrysanthemumate, both with and without thesynergist, in this example butyl B-butynyl phenylphosphonate, asfollows:

With Without Synergist Synergist (l-Cyclohexene-l ,2-dicarboximido)-0.140 g 0.140 g methyl chrysanthemumate(% active) Butyl 3-butynylphenylphosphonate 0.625 g none Heavy aromatic naphtha 6.00 g 6.00 gPurified kerosene 3.24 g 186 g Trichloromonofluoromethane 20.00 g 20.00g Dichlorodifluoromethane 20.00 g 20.00 g

A group of 200 to 300 houseflies was introduced into a 216 cu ft. testchamber, prepared according to the specifications of the ChemicalSpecialities Manufacturers Association (Soap and Chemical Specialities,1961 Blue Book, p. 244). Measured amounts of the aerosol formulationswere introduced into the chamber. Results, shown in Table 8, are theaverages of nine replicates for the composition containing the synergistand to two replicates for the composition containing thechrysanthemumate alone.

Table 8 Aerosol Formulations Composition Average Dose KnockdownMortality (q/lOOOft) 15 minutes 24 hours With Synergist 3.15 g 84% 71%Without Synergist 2.92 g 85% 14% phonate; 2-propenyl 2-ethyl-3-butynyl(2-phenylpropyl )pho sphon ate; 2-methylbutyl 3-butynyl (4-iodobenzyl)phosphonate; methyl 3-methyl-4- pentynyl(2,3-dichlorobenzyl)phosphonate; 2-propenyl l-methyl-3-butynyl(2-pyridyl)methylphosphonate; 2- methoxypropyl l-ethyl-2-propynylphenylphosphonate; methyl 1-ethyl-3-butynyl benzylphosphonothionate;n-propyl (2-methyl-3-butynyl) (3-fluorobenzyl)- phosphonate; i-amyl3-butynyl (2- pyrid yl)phosphonate; Z-methoxyethyl 2-propynylphenylphosphonothionate; n-hexyl l-ethyl-2-propynyl(4-chlorobenzyl)phosphonate; and the like.

The novel synergists of this invention may be prepared by adaptation ofthe synthetic procedures illustrated above, i.e., from suitablephosphonochloridates or phosphinates as well as by other knownprocedures. These procedures are well described in the chemicalliterature, for example by Kosalopoff, J.A.C.S. 72, 4292 (1950); Hudsonet al. J. Chem. Soc., 1859 (1960); Harman et al, US. Pat. No. 2,659,714;Bentov et a1. .1. Chem. Soc., 4750 (1964); and Cherbuliez et al, Helv.Chim. Acta, 46, 2464 (1963).

The novel synergists described herein have a degree of effectiveness notshared by certain closely related compounds. The nature and location ofthe unsaturated linkage has been found to have a marked effect on thesynergistic effectiveness of this class of compounds. For example,reduction of the acetylenic linkage to an olefinic or a saturatedlinkage diminishes the synergistic activity. Displacement of theacetylenic 16 linkage from the terminal position also decreases theactivity.

The synergistic compositions of this invention may be employed tocontrol a variety of crop pests and household pests. These compositionsare not usually applied full strength, but, are generally incorporatedwith the adjuvants and carriers normally employed for facilitatingdispersion of active ingredients for insecticidal applications,recognizing the accepted fact that the formulation and mode ofapplication may affect the activity of a material. Striking results areobtained when these compositions are applied as space sprays and aerosolsprays, for example, or are formulated into any of the diluted andextended types of formulations used in insecticidal practice, includingdusts, wettable powders, emulsifiable concentrates, solutions,granulars, baits, and the like, for application to foliage, withinenclosed areas, to surfaces, and wherever insect control is desired.

These synergistic compositions may be made into liquid concentrates bysolution or emulsification in suit able liquids, and into solidconcentrates by admixing the active components with a talc, clays, andother solid carriers used in the insecticide art. Such concentratesnormally contain about 580% of the toxic composition, and the rest inertmaterial which includes dispersing agents, emulsifying agents, andwetting agents. For practical application, the concentrates are normallydiluted with water or other liquid for liquid sprays, with liquefiedpropellants for aerosols, or with additional solid carrier forapplication as a dust or granular formulation. Baits are usuallyprepared by mixing such concentrates with a suitable insect food, suchas mixtures of cornmeal and sugar, and insect attractants may also bepresent. The concentration of the active ingredients in the dilutedformulations, as generally applied for control of insects, is normallyin the range of about 0.001% to about 5%. Many variations of sprayingand dusting compositions are well known in the art, as are thetechniques for formulating and applying these compositions.

Employing the synergistic pesticidal compositions described herein,enhanced control is obtained of both crop and household pests, includinginsects and acarids against which the cyclopropanecarboxylates arethemselves effective, but at higher concentrations. This includes flyingand crawling pests of the orders Coleoptera (beetles), Hemiptera (truebugs), Homoptera (aphids), Diptera (flies), Orthoptera (roaches),Acarina (mites and ticks), and Lepidoptera (butterflies and mothsincluding their larvae). Because of the low mammalian toxicity of thesecompositions, they are preferred to compositions for use in control ofpests in an environment inhabited by man and animals, including controlflies, mosquitoes, ants, roaches, moths, ticks, and the like, as well asin uses such as packaging, food and grain protection, and garden, pet,and livestock uses.

The relative amounts of synergist and chrysanthemumate employed are notcritical, in that a relatively minor amount, e.g., less than one part ofsynergist per part of chrysanthemumate, is effective in imparting abeneficial effect to the combination. From practical considerations, itis preferred to use larger amounts of synergist, for examplefrom 2 to 50parts of synergist per part of cyclopropanecarboxylate. Even largerproportions of synergist may be employed without detriment, whether ornot the optimum synergistic proportions have been achieved. It is clearthat effective amounts of synergist should be employed in thecompositions, that the components should be present in synergisticproportions, and that effective amounts of the compositions, to controlthe particular insect pests in the environment of infestation, should beapplied.

It is apparent that many modifications may be made in the formulationand application of the compositions of this invention, without departingfrom the spirit and scope of the invention, and of the following claims.

We claim:

1. An insecticidal and acaricidal composition comprising andinsecticidally and dicaricidally effective amount of a combination of A.an insecticidal cyclopropanecarboxylate the insecticidal activity ofwhich is synergized by B. a synergistically effective amount of acompound of the formula OR C CH wherein R is selected from the groupconsisting of alkyl and alkenyl having one to six carbon atoms; and R isalkylene of one to four carbon atoms; wherein the ratio of AB is in therange of 1:2 to 1:50.

2. The insecticidal and acaricidal composition of claim 1 wherein saidcyclopropanecarboxylate is allethrin.

3. The insecticidal and acaricidal composition of claim 1 wherein saidcyclopropanecarboxylate is pyrethrins.

4. The insecticidal and acaricidal composition of claim 1 wherein saidcyclopropanecarboxylate is (lcyclohexene-l ,2-dicarboximido)methyl2,2-dimethyl- 3-( 2-methyll -propenyl )cyclopropanecarboxylate.

5. The insecticidal and acaricidal composition of claim 1 wherein saidcyclopropanecarboxylate is 18 Y (5 -benzyl-3-furyl )methyl 2,2,3,3-tetramethylcyclopropanecarboxylate.

6. A method of controlling insect and acarid pests which comprisesapplying thereto an insecticidally and acaricidally effective amount ofa composition com- .prising:

A. an insecticidal cyclopropanecarboxylate the insecticidal activity ofwhich is synergized by B. a synergistically effective amount of acompound of the formula o H 0R1 P ORZCECH wherein R is selected from thegroup consisting of alkyl and alkenyl having one to six carbon atoms;and R is alkylene of one to four carbon atoms; wherein the ratio of ABis in the range of 1:2 to 1:50.

7. The method of claim 6 wherein the cyclopropanecarboxylate is selectedfrom the group consisting of allethrin, pyrethrins,(Lcyclohexene-l,2-dicarboximido )methyl 2,2-dimethyl-3-( 2-methyllpropenyl)cyclopropanecarboxylate, and (5-benzyl-3- furyl)methyl2,2,3,3-tetramethylcyclopropanecarboxylate.

8. The method of claim 6 wherein the cyclopropanecarboxylate isl-cyclohexene-l ,Z-dicarboximido )methyl 2,2-dimethyl-3-( 2-methyllpropenyl)cyclopropanecarboxylate.

9. The method of claim 6 wherein said synergistic compound is n-propyl2-propynyl phenylphosphonate.

10. The method of claim 6 wherein said synergistic compound is n-butyl3-butynylphenylphosphonate.

11. The method of claim 1 wherein the cyclopropanecarboxylate is(5-benzyl-3-furyl)methyl 2,2,3,-

3-tetramethylcyclopropanecarboxylate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT N0.3,885,031

DATED May 20, 1975 INVENTOR(S) Ronald Eugene Montgomery and Harry HobartIncho It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Column 5, line 39, "not Water bath" should read "hot water bath".

Column 9, line 57, "products" should read "product". Column 9, line 59,first word should read "bath" not "both". Column 13, lines 67 and 68should follow Table 6 rather'than Table 7. I In claim 1, column 17, line14, "prising and insecticidally and dicaricidally effective" should read"prising an insecticidally and acaricidally effective".

Signed and Sealed this [SEAL] fifteenth D3) of June 1976 A ttest:

ZXI'IIlDQZIA SON C. MARSHALL DANN 1g flu-er (mnmin ioner nfParems andTrademark

1. AN INSECTICIDAL AND ACARICIDAL COMPOSITION COMPRISING ANDINSECTICIDALLY AND DICARICIDALLY EFFECTIVE AMOUNT OF A COMBINATION OF A.AN INSECTICIDAL CYCLOPROPANECARBOOXYLATE THE INSECTICIDAL ACTIVITY OFWHICH IS SYNERIZED BY B. A SYNERGISTICALLY EFFECTIVE AMOUNT OF ACOMPOUND OF THE FORMULA
 2. The insecticidal and acaricidal compositionof claim 1 wherein said cyclopropanecarboxylate is allethrin.
 3. Theinsecticidal and acaricidal composition of claim 1 wherein saidcyclopropanecarboxylate is pyrethrins.
 4. The insecticidal andacaricidal composition of claim 1 wherein said cyclopropanecarboxylateis (1-cyclohexene-1,2-dicarboximido)methyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopRopanecarboxylate.
 5. Theinsecticidal and acaricidal composition of claim 1 wherein saidcyclopropanecarboxylate is (5-benzyl-3-furyl)methyl2,2,3,3-tetramethylcyclopropanecarboxylate.
 6. A method of controllinginsect and acarid pests which comprises applying thereto aninsecticidally and acaricidally effective amount of a compositioncomprising: A. an insecticidal cyclopropanecarboxylate the insecticidalactivity of which is synergized by B. a synergistically effective amountof a compound of the formula
 7. The method of claim 6 wherein thecyclopropanecarboxylate is selected from the group consisting ofallethrin, pyrethrins, (1-cyclohexene-1,2-dicarboximido)methyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate, and(5-benzyl-3-furyl)methyl 2,2,3,3-tetramethylcyclopropanecarboxylate. 8.The method of claim 6 wherein the cyclopropanecarboxylate is(1-cyclohexene-1,2-dicarboximido)methyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate.
 9. Themethod of claim 6 wherein said synergistic compound is n-propyl2-propynyl phenylphosphonate.
 10. The method of claim 6 wherein saidsynergistic compound is n-butyl 3-butynyl phenylphosphonate.
 11. Themethod of claim 1 wherein the cyclopropanecarboxylate is(5-benzyl-3-furyl)methyl 2,2,3,3-tetramethylcyclopropanecarboxylate.